Amphiphilic compounds with at least two hydrophilic and at least two hydrophobic groups based on dicarboxamides

ABSTRACT

The invention concerns amphiphilic compounds of general formula (I), in which R 1  and R 3  each represent a C 1  -C 22  hydrocarbon residue, R 2  is a spacer and X and Y are functional groups. The proposed compounds have at least two hydrophilic and at least two hydrophobic groups based on dicarboxylic acid diamides. The amphiphilic compounds according to the invention are mostly surface-active and are especially suitable for use as emulsifiers, demulsifies, detergents, dispergents and hydrotropic agents in industry and households, for example, in the treatment of metals, ore processing, surface finishing, washing, cleaning, cosmetics, medicine and food processing and preparation.

This application is a 371 of PCT/EP95/04530, filed Nov. 17, 1995.

The invention relates to amphiphilic compounds with at least twohydrophilic and at least two hydrophobic groups based on diamides.

A wide variety of anionic, cationic or nonionic and zwitterioniccompounds are known as amphiphilic substances. By far the most of thesesubstances consist of a hydrophilic head group and at least onehydrophobic part.

With the amphiphilic substances there is a need, for ecological reasons,for example concerning the reduction in the cost of packaging andtransport, to achieve an increasingly greater effect per mass ofsubstance employed. Since optimization by mixing amphiphilic substancesproduces only very limited advances, novel amphiphilic substances withgreater efficiency are required. It is therefore necessary in particularto find substances with lower critical micelle concentrations and/orlower surface and interfacial tensions in order to be able to reducemarkedly the amounts of active substance.

Initial approaches to a solution in this direction by doubling one partof the structure (hydrophilic head group, hydrophobic group) havealready been disclosed. Thus, cationic surface-active compounds can beobtained by adding long-chain alkyl halides onto permethylatedalkylenediamines [R. Zana, M. Benrraou, R. Rueff, Langmuir, 7 (1991)1072: R. Zana, Y. Talmon, Nature, 362 (1993) 228; E. Alami, G. Beinert,P. Marie, R. Zana, Langmuir, 9 (1993) 1465].

Anionic surface-active compounds with at least two hydrophilic and atleast two hydrophobic groups have to date been prepared only on thebasis of diglycidyl ethers (U.S. Pat. No. 5,160,450, JP 01 304 033, JP 4124 165). However, diglycidyl ethers are regarded as toxicologicallyobjectionable and are rather costly. Furthermore, epichlorohydrin isused for their preparation, which leads to large amounts of residues sothat these compounds are no longer in accord with the times from theecotoxicological and economic viewpoints.

The object therefore was to find amphiphilic compounds which have atleast two hydrophilic and at least two hydrophobic groups, theamphiphilic compounds having a very high efficiency relative to theamount used, and which furthermore can be prepared from raw materialswhich are easily available industrially and without large amounts ofunwanted by-products being formed.

The object is achieved according to the invention by amphiphilicdiamides whose basic skeleton can be prepared from dicarboxylic acids ortheir esters and amines. The corresponding di- or oligoamides can bealkoxylated. These nonionic amphiphilic compounds can be converted intoanionic amphiphilic compounds by, for example, reacting theabovementioned compounds with SO₃ /inert gas (or oleum chlorosulfonicacid or sulfamic acid), with polyphosphoric acid, with a haloaceticacid, with a sultone, with maleic anhydride and sodium bisulfite or witha taurine and, in each case, subsequently neutralizing.

The amphiphilic compounds according to the invention are thereforecompounds of the general formula I ##STR2## where R¹, R², R³, X and Y informula I have the meanings described below:

R¹ and R³ are, independently of one another, an unbranched or branched,saturated or unsaturated hydrocarbon radical with 1 to 22, preferably 7to 17, carbon atoms.

Specific substituents R¹ and R³ which may be mentioned are the radicalsmethyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl,n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl,n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl,n-eicosyl, n-uneicosyl, n-docosyl and their branched-chain isomers, andthe corresponding singly, doubly or triply unsaturated radicals.

R² is a spacer consisting of an unbranched or branched chain with 2 to100 carbon atoms, which contains 0 to 20 oxygen and/or 0 to 20 nitrogenatoms and/or 0 to 4 sulfur atoms and/or 0 to 3 phosphorus atoms, andwhich has 0 to 20 functional side groups.

The spacer R² is, in particular,

unbranched or branched alkylene chains of the formula II as basicskeleton

    --C.sub.a H.sub.2a --                                      (II)

with a=2 to 18, preferably a=3 to 6;

unbranched or branched alkenylene chains of the formula III as basicskeleton

    --C.sub.b H.sub.2b --CH|CH--C.sub.c H.sub.2c --   (III)

with b+c=2 to 16, where b and c are each greater than zero;

unbranched or branched alkynylene chains of the formula IV as basicskeleton

    --C.sub.d H.sub.2d --C.tbd.C--C.sub.e H.sub.2e --          (IV)

with d+e=2 to 16, where d and e are each greater than zero, and where inthe compounds according to formulae II to IV the spacer contains at anydesired point in the chain additionally 0 to 4 carbonyl, carboxyl, aminoor acylamino groups;

alicycles according to the formula V

    --C.sub.f H.sub.2f --cyclo C.sub.6 H.sub.10 --C.sub.g H.sub.2g --(V)

with f and g = each 1 to 6 or according to formula VI

    --3(4),8(9)-di(methylene)-tricyclo[5.2.1.0.sup.2.6 ]decane- (VI);

unsubstituted or substituted aromatics according to the formula VII

    --C.sub.h H.sub.2h --C.sub.6 R.sub.4 --(C.sub.i H.sub.2i --C.sub.6 R.sub.4).sub.j.sbsb.1 --C.sub.j.sbsb.2 H.sub.2j.sbsb.2 -- (VII)

or according to the formula VIII

    --C.sub.h H.sub.2h --C.sub.10 R.sub.6 --C.sub.j H.sub.2j --(VIII)

with h, j, j₁ and j₂ = each 0 to 8 and i=1 to 8 and with R=independentlyof one another in each case H or C₁ - to C₄ -alkyl;

a chain with 0 to 20 functional side groups, where the functional sidegroups consist of amino, acylamino, carbonyl, carboxyl or hydroxylgroups, and/or 0 to 4 rings, which are isolated or fused.

Furthermore, the spacer R² contains in each case 0 to 20, preferably 1to 12, oxygen and/or nitrogen atoms, 0 to 4 sulfur atoms and 0 to 3phosphorus atoms.

R² thus furthermore has in particular the meaning

of a compound according to the formula IX

    --C.sub.k H.sub.2k --C.sub.x R.sub.y --Z--C.sub.x R.sub.y --C.sub.1 H.sub.21 --                                               (IX)

with k and l = each 0 to 8, x=6 and y=4 or x=10 and y=6 or x=14 and y=8,and Z=O, CO, NH, NR¹, N--C(O)R¹, SO₂, where R¹ is a hydrocarbon radicalwith 1 to 22 carbon atoms and R are, independently of one another, ineach case H or C₁ - to C₄ -alkyl;

of a compound according to the formula X

    --C.sub.m H.sub.2m --(OC.sub.n H.sub.2n).sub.p --C.sub.q H.sub.2q --(X)

m=1 to 4, n=2 to 4, p=1 to 20, preferably p=1 to 6 and q=1 to 4, wheremixed alkoxide units may also occur and then the sequence of thealkoxide unit is arbitrary;

of a compound according to the formula XI

    --C.sub.r H.sub.2r (RNC.sub.s H.sub.2s).sub.t --C.sub.u H.sub.2u --(XI)

or according to the formula XII

    --[C.sub.r H.sub.2r [RN--C(O)--NR].sub.t --C.sub.u H.sub.2u ].sub.w --(XII)

or according to the formula XIII

    --[C.sub.r H.sub.2r [RNC(O)C.sub.v H.sub.2v C(O)NR].sub.t --C.sub.u H.sub.2u ].sub.w --                                       (XIII)

or according to the formula XIV.0

    --[C.sub.r H.sub.2r [RN--C(O)--CH═CH--C(O)--NR].sub.t --C.sub.u H.sub.2u ].sub.w --                                       (XIV)

or according to the formula XV

    --[C.sub.r H.sub.2r [RNC(O)C.sub.x R.sub.y C(O)NR].sub.t C.sub.u H.sub.2u ].sub.w --                                                (XV)

with r=2 to 4, s=2 to 4, t=1 to 20, preferably t=1 to 4, u=2 to 4, v=0to 12, w=1 to 6, x=6 and y=4 or x=10 and y=6 or x=14 and y=8 withR=independently of one another in each case H or C₁ - to C₄ -alkyl.

X and Y are, independently of one another, functional groups inparticular substituents of the formula XVI

    --(C.sub.2 H.sub.4 O).sub.α (C.sub.3 H.sub.6 O).sub.β H(XVI)

with α=0 to 50, preferably α=10 to 30, β=0 to 60, preferably β=20 to 40,

and α+β=1 to 100, preferably α+β=10 to 50, where R² is not C₂ H₄ whenβ=0.

and where with mixed alkoxides the alkoxide units are incorporatedrandomly or blockwise and the sequence is arbitrary,

or substituents of the formula XVII

    --(C.sub.2 H.sub.4 O).sub.γ (C.sub.3 H.sub.6 O).sub.δ --FR(XVII)

with in each case

γ=0 to 20, preferably γ=0 to 8,

δ=0 to 20, preferably δ=0 to 12,

and γ+δ=1 to 40, preferably γ+δ=5 to 20, where RF is a functionalradical --CH₂ --COOM, --SO₃ M, --P(O)(OM)₂,

--O--C(O)--C₂ H₃ (SO₃ M)--CO₂ M'or --C₂ H₄ --SO₃ M with M, M'=alkalimetal, ammonium, alkanolammonium or 1/2 alkaline earth metal, orsubstituents of the formula XVIII

    --CH.sub.2 [CHO(C.sub.2 H.sub.4 O).sub.ε (C.sub.3 H.sub.6 O).sub.η A].sub.z --CH.sub.2 --O(C.sub.2 H.sub.4 O).sub.μ (C.sub.3 H.sub.6 O).sub.ρ --A                                  (XVIII)

with z=3 to 6, preferably z=4 and ε or μ=0 to 30, preferably ε or μ=0 to10, and η or ρ=0 to 30, preferably η or ρ=0 to 10, and where thealkoxide units are likewise incorporated randomly or blockwise and thesequence is arbitrary and where A is H or FR.

The degree of alkoxylation is in each case an average and can assume anydesired, including non-integral, value within the stated limits.

The amphiphilic compounds according to the invention are usuallydistinguished by extremely low critical micelle concentrations (CMC) andvery low surface and interfacial tensions (for example in the presenceof paraffin), which must be ascribed to their special structure--atleast two hydrophilic groups and at least two hydrophobic groups.Furthermore, most of them display a rather high hydrophilic suspensioncapacity which is about halfway between that of conventional surfactantsand that of pentasodium tripolyphosphate. Some of these compounds areextremely rapid wetting agents.

The amphiphilic compounds according to this invention are particularlysuitable as emulsifiers, demulsifiers, detergents, dispersants andhydrotropes in industry and domestically, for example in the areas ofmetal processing, ore production, surface treatment, washing andcleaning, cosmetics, medicine and foodstuff processing and preparation.

In these cases they can be combined with all customary anionic,nonionic, cationic and ampholytic surface-active substances. Examples ofnonionic surface-active substances which can be used for a combinationand which may be mentioned are: fatty acid glycerides, fatty acidpolyglycerides, fatty acid esters, ethoxylates of higher alcohols,polyoxyethylene fatty acid glycerides, polyoxyethylene/propylene glycolfatty acid esters, polyoxyethylene sorbitan fatty acid esters,polyoxyethylene castor oil or hardened castor oil derivatives,polyoxyethylene lanolin derivatives, polyoxyethylene fatty acid amides,polyoxyethylene alkylamines, alkanolamines, alkylamine oxides,derivatives of protein hydrolysates, hydroxy-mixed ethers, alkylpolyglycosides and alkylglucamides.

Examples of anionic surface-active substances which can be used forcombinations and which may be mentioned are: soaps, ether carboxylicacids and salts thereof, alkylsulfonates, α-olefinsulfonates, sulfonatesof higher fatty acid esters, alcohol sulfates, alcohol ether sulfates,hydroxy-mixed ether sulfates, salts of phosphate esters, taurides,isethionates, linear alkylbenzenesulfonates, cumenesulfonate,alkylarylsulfonates, sulfates of polyoxyethylene fatty acid amides andsalts of acylamino acids.

Examples of customary cationic surface-active substances which can beused for combinations and which may be mentioned are:alkyltrimethylammonium salts, dialkyldimethylammonium salts,alkyldimethylbenzylammonium salts, alkylpyridinium salts,alkylisoquinolinium salts, benzethonium chlorides and cationic acylaminoacid derivatives.

Examples of ampholytic surface-active substances which can be used forcombinations and which may be mentioned are: amino acids, betaines,sulfobetaines, imidazoline derivatives, soya oil lipids and lecithin.

Furthermore, the amphiphilic compounds according to the invention canalso be combined together on their own.

It is likewise possible to add conventional additives to the amphiphiliccompounds according to the invention. Such additives are specificallyselected for a formulation and normally comprise inorganic salts such assodium chloride and sulfate, and builders, hydrotropes, UV absorbers,softening agents, chelating agents, viscosity modifiers and fragrances.

The abovementioned compounds can be prepared by known methods:

The dicarboxylic acids or their methyl esters are reacted with twoequivalents of amine at elevated temperatures (80 to 240° C.) optimallyin the presence of a catalyst, with the water or methanol which isproduced being removed under vacuum.

N,N'-Dialkyldicarboxamides are alkoxylated at temperatures from 130 to190° C. under pressure in the presence of a basic catalyst. This step isoptional for dialkylpolyhydroxydicarboxamides (formula XVIII).

The products can subsequently be reacted with SO₃ /inert gas (oleum,chlorosulfonic acid or sulfamic acid) or polyphosphoric acid or with ahaloacetic acid, a sultone, with maleic anhydride and sodium bisulfiteor with isethionic acid and be neutralized with aqueous alkali metal oralkaline earth metal hydroxides or ammonia or alkanolamines.

What is claimed is:
 1. An amphiphilic compound of the formula (I):##STR3## wherein R¹ and R³ are, independently of each other, a branchedor unbranched, saturated or unsaturated hydrocarbon radical with 1 to 22carbon atoms;R² is a spacer, which is an unbranched or branched alkylenechain of the formula (II):

    --C.sub.a H.sub.2a                                         (II)

wherein a is from 2 to 18, or an unbranched or branched alkenylene chainof the formula (III):

    --C.sub.b H.sub.2b --CH═CH--C.sub.c H.sub.2c --        (III)

wherein b+c is from 2 to 16, where b and c are each greater than 0, orof an unbranched or branched alkynylene chain of the formula (IV):

    --C.sub.d H.sub.2d --C.tbd.C--C.sub.e H.sub.2e             (IV)

wherein d+e is from 2 to 16, where d and e are each greater than 0, andwherein in the compounds of formulae (II) to (IV), the spacer containsat any desired point in the chain additionally up to four functionalside groups, comprising amino, acylamino, carbonyl, carboxyl orhydroxyl, or up to 4 rings, which are isolated or fused, or both; and Xand Y are, independently of each other, substituents of the formula(XVI):

    --(C.sub.2 H.sub.4 O).sub.α (C.sub.3 H.sub.6 O).sub.β H (XVI)

wherein α is 0 to 50; β is 0 to 60; and α+β is 1 to 100; wherein R² isnot C₂ H₄, when β is 0; and wherein with mixed alkoxides, the alkoxideunits are incorporated randomly or blockwise and the sequence isarbitrary; or wherein X and Y are, independently of one another,substituents of the formula XVII:

    --(C.sub.2 H.sub.4 O).sub.γ (C.sub.3 H.sub.6 O).sub.δ --FR (XVII)

with in each caseγ being 0 to 20, δ being 0 to 20, and γ+δ being 1 to40, where FR is a functional radical --CH₂ --COOM, --SO₃ M, --P(O)(OM)₂,--O--C(O)═C₂ H₃ (SO₃ M)--CO₂ M', or --C₂ H₄ --SO₃ M with M, M' beingalkali metal, ammonium, alkanolammonium, or 1/2 alkaline earth metal, orsubstituents of the formula XVIII:

    --CH.sub.2 (CHO)(C.sub.2 H.sub.4 O).sub.ε (C.sub.3 H.sub.6 O).sub.η A).sub.x --CH.sub.2 --O(C.sub.2 H.sub.4 O).sub.μ (C.sub.3 H.sub.6 O).sub.ρ --A                                  (XVIII)

wherein z is 3 to 6; ε or μ are 0 to 30; and η or ρ are 0 to 30; andwhere A is H or FR and wherein with mixed alkoxides, the alkoxide unitsare likewise incorporated randomly or blockwise and the sequence isarbitrary, and wherein at least one of X and Y contains the FRfunctional radical.
 2. The amphiphilic compound of claim 1 wherein thehydrocarbon radicals R¹ and R³ in the formula I contain, independentlyof one another, 7 to 17 carbon atoms.
 3. The amphiphilic compound ofclaim 1 wherein the spacer R² contains 0 to 20, oxygen or nitrogen atomsor 0 to 4 sulfur atoms or 0 to 3 phosphorus atoms or a combinationthereof.
 4. The amphiphilic compound of claim 1, wherein α is 10 to 30;β is 20 to 40; and α+β is 10 to
 50. 5. The amphiphilic compound of claim1, wherein z is 4; ε or μ is each 0 to 10; and η or ρ is each 0 to 10.6. The amphiphilic compound of claim 2, wherein R¹ and R³ each havetwelve carbon atoms, and R² is either --C₂ H₄ -- or --C₄ H₈ --, and Xand Y contain a total of twelve ethylene oxide groups, each having sixof said groups, and which further contain --SO₃ Na functional groups. 7.A method of emulsifying or demulsifying a liquid, which comprises addingone or more of the amphiphilic compounds of claim 1 to said liquid.
 8. Amethod of metal processing, ore production or surface treatment, whichcomprises effecting said metal processing, ore production or surfacetreatment with one or more of the amphiphilic compounds of claim
 1. 9. Amethod of cleaning or washing textiles, which comprise cleaning orwashing textiles with one or more of the amphiphilic compounds ofclaim
 1. 10. A method of cleaning hand surfaces, which compriseseffecting said cleaning with one or more of the amphiphilic compounds ofclaim
 1. 11. A method of cleaning or washing skin or hair or both, whichcomprises effecting said cleaning or washing with one or more of theamphiphilic compounds of claim 1.